with higher melting-points confirms the view that the errors introduced by the extrapolation are very slight, and we feel confident in the practical accuracy of our statement. The total energy possessed by the hydrogen and oxygen at -273° C. is probably very much more than 67,300 calories, and may be many times that amount, for we have noevidence whatever as to the energy which the ice possesses at that temperature. We only know that the energy of the ice is 67,300 calories less than the amount possessed by the equivalent hydrogen and oxygen before the combination. The ice may, and in our opinion certainly does, possess a vast amount of energy. Its store of energy is perhaps comparable to that possessed by radium. In what form does the 67,300 calories of energy possessed by the 34'78 cc. of hydrogen and oxygen at -273° C. exist? The answer to the question, "What is energy? and "What is matter?" must both be given before any sufficient answer to the first question could be made. But there is certainly no harm in stating what we do know concerning the answer to that question, and it is this :If the same mechanical laws which govern larger masses of matter and energy at higher temperatures apply to the hydrogen and oxygen at -273° C., then a stable system could not exist if all of the energy were kinetic, or if all of the energy were potential, but some portion of the energy must be potential and some portion must be kinetic (see Meyer, "Kinetic Theory of Gases," p. 344, English translation of second revised edition). There has never been the slightest evidence produced to show that these mechanical laws do cease to hold at -273° C., or with small sub-divisions of mass, and therefore we think it probable that at -273° C. the small particles-atoms if you please to call them so-of hydrogen and oxygen, are in exceedingly rapid motion, and are held together by some force which gives rise to a potential energy. The force we will call chemical affinity, and the energy we will call chemical energy. It is not out of place to point out here, for it is very suggestive, that if we have two masses of matter which attract each other inversely as the square of their distance apart, and which form a stable system, they will revolve around their common centre of gravity, and they cannot give out a greater amount of energy than they retain as kinetic energy. Just what relation would hold if we had numerous particles governed by the same laws, mathematics has not yet proved adequate to reveal. The relation may be a very simple one in spite of the mathematical complexity of the problem. The answer to our first question is therefore that 67,300 calories of the total energy possessed by the 2016 grms. of hydrogen and the 16 grms. of oxygen at o° C. existed in some form in those substances at -273° C., and 4097 calories of energy were added in raising those substances to o° C. and changing them to the gaseous condition. Energy Changes caused by a Rise in Temperature. We wish next to show why 4097 calories of energy were necessary to change the temperature and condition of the hydrogen and oxygen as described. Of this amount of energy 2125 calories were added to the hydrogen. Now the hydrogen at -273° C. originally Occupied a volume of 24'18 cc., and at o° C. it occupied a volume of 22,431 CC. This expansion necessitated the expenditure of work in pushing back the atmosphere. The work so done we will call Ee, and it may be cal culated for 1 grm. from the equation (see Note)— E = 0.000031833 P (V−v) calories . . (I), where P is the pressure in mm. of mercury, and V is the final and the original volume. For hydrogen, therefore, the external work performed during the expansion is 0'000031833 × 760 (11,126′4 — 12′1) 2'016 542'1 calories. = = 19. (NOTE. The constants used in this paper are :-Density of mercury 13.5956 at o° referred to water at 4° C.; attraction of gravity 980 5966 at latitude 45° and sealevel; atomic weight of oxygen 16.00; density of hydrogen at latitude 45° and sea-level 0.0000898765. This is an average of the values given by Morley, ("Smithsonian Contributions to Knowledge," No. 980), and the value given by Rayleigh (Proc. Roy. Soc., liii., 147, No. 322), after reduction to latitude 45°. Rayleigh's value was an average of his own value, that of Leduc, and the value of Regnault as corrected by Crafts. The unit calorie is taken as from 15° to 16° C., and as equal to 41,880,000 ergs. This is Rowland's value as corrected by Day-Phys. Rev., 1898, vi., 194; see also Ber. Deut. Phys. Ges., vi., 578). During the expansion of the hydrogen the molecules of the hydrogen were moved further apart, and a certain amount of energy was necessary to overcome the attracenergy, which we will denote by Ea, may be calculated, tion between the hydrogen molecules. This amount of as the author has shown in a series of papers,* from the equationEa' (3/d3/D) calories... (2) where d and D are the density in the original and final conditions respectively, and u' is a constant which may be obtained from the following equation: : (3). Here L is the heat of vaporisation, E is the energy spent in pushing back the atmosphere during the vaporisation, and is calculated from Equation 1, d is the density of the liquid, and D the density of the saturated vapour at the temperature of vaporisation. To calculate u' for hydrogen, L 123.1 calories. The density of the liquid at its boiling-point has been determined by Dewar as 0·070025, corresponding to a volume of 14 28 cc. per grm. The density of the saturated vapour may be calculated on the supposition that it obeys the gas laws, the error so introduced being negligible. The equation for this calculation is : D= 0.000016014 Pm T 3 Since T is 20'41°, D becomes o'001202, and the corresponding volume is 8319 cc. From Equation 1, Eɛ is found to be 19.78 calories, and L- Es is therefore 103.32. Dividing this by the value of 3 d- vD, namely, 0.3059, we have for ' the value 337'7. Substituting this value in Equation 2, and using for d the density of hydrogen at -273° C. as given by Dewar, o'08272, and for Ď the value already given at o° under standard conditions, namely, 0.00008988, we have finally, Ea=337'7X0*3909 × 2·016 = 266'1 calories. It is not necessary to pause here to defend the kinetic theory of gases. That theory represents the attempt to extend the mechanical laws which govern large masses of matter to smaller particles of the same material. Its foundation upon these mechanical laws is quite as secure as are the foundations of any system of thermodynamics yet advanced-both theories alike resting upon observed laws to which no single exception has ever been found. Moreover, it has led to important discoveries and correlated numerous facts. Making use now of the kinetic theory, it is easy to calculate the energy necessary to add to the grm. molecular *Journ Phys. Chem., 1902, vi., 209; 1904, viii., pp. 383, 593; 1905, ix., 402; 1906, x., 1; 1907, xi., pp. 132, 594. The equation has been proved to hold for liquids as they expand to the volume of the saturated vapour. The author believes that the equation, which was theoretically derived, may be applied as above, and the result appears to justify the belief. Whence the kinetic energy of the grm. molecular weight of hydrogen at o° C. is 8140 calories. We know also from the kinetic theory of gases that whenever we increase the kinetic energy of a molecule we at the same time increase its internal energy, which we will call E. The increase in the internal energy is proportional to the increase of the kinetic theory, and its amount may be calculated from the relation first proposed by Waterston, namely, — specific heat of gas at constant pressure specific heat of gas at constant volume Sp 3/2 R+E+R 5/2 R+E1 Sv 3/2 R+E 3/2 R+E, Now putting in the place of R its value 2/3 = = Energy necessary to overcome external .... Energy necessary to overcome mole- Energy necessary for translational motion.. Energy necessary for internal work Total.. = Calories. 16.89 = = 53.62 25'44 16.69 To effect the above mentioned change for 16 grms. of oxygen will require 1802 calories. The amount actually added to the oxygen was found to be 1972 calories. The divergence here, amounting to about 10 calories per (6). gr., cannot, we believe, be considered as entirely due to experimental error, and we have made an extended investigation as to its cause. As a result of this investigation, the details of which it would be impossible to reproduce within the limits of this paper, we believe that besides the Ek and so-called external, attractive, kinetic, and internal energy, " T for which allowance has been made, all bodies, while in the solid condition, require yet an additional amount of to 1 :energy, the exact office of which we are unable to explain. The amount of this unaccounted for energy varies with the absolute temperature of the melting-point of the body. In the case of hydrogen because of its very low melting. point, 14° absolute, the amount thus unaccounted for was But with well within the limit of experimental error. oxygen this is not the case. We are led here to add that the total energy necessary to change a solid monatomic element from -273° to the liquid condition at its melting-point, appears to us to be three times the kinetic energy of translation required by the element at that temperature; or, in other words, 8'94 T calories, where T is the absolute temperature of the melting-point. Prof. J. W. Richards (Trans. American Electrochem. Soc., 1908, xiii., 447) has reached nearly the same conclusion, considering the total heat in the molten metal at its melting point to be 10 T calories. We will publish our data and conclusions upon this subject later. Unfortunately our calculations cannot be extended to water, for it is an associated substance. Except for the discrepancy of 170 calories, we have shown why and how the 4097 calories of energy added to the hydrogen and oxygen to change them from their condition at -273° C. to their condition at o° C. were expended, and have therefore, in part at least, answered the second question as to why and how the amount of heat given out by the reaction of the hydrogen and oxygen will vary under different conditions of volume, temperature, and pressure. The Chemical Changes involved in the Reaction. The answer to the third question, as to why the reaction did not take place when the hydrogen and oxygen were first mixed, and before the passage of the electric spark, has doubtless occurred to everyone. It was first necessary to loosen the union of some of the hydrogen atoms from their combination with other hydrogen atoms, and the union of some of the oxygen atoms from their combination with other oxygen atoms. Then, once free, the hydrogen atoms and the oxygen atoms unite, and in so doing give out enough heat to loosen the neighbouring hydrogen and oxygen molecules, and these in their turn unite, and thus the reaction is propagated. But it is perhaps not so clearly recognised, that the force which we call chemical affinity is probably never directly affected by a rise in temperature. Certainly in the case under consideration we have accounted for all of the energy added to the hydrogen and the oxygen from -273° to o° C., save 170 calories, as having been used to effect CHEMICAL NEWS, Jan. 12, 1912 Absorption Spectra of Quinine, &c. external work, overcome molecular attraction, and effect an increase in the translational and internal motion of the molecules, and the original 67,300 calories possessed at 273° C. appears to have been held, intact as it were, neither increased nor diminished, by the changes of temperature, pressure, and volume necessary to raise the hydrogen and oxygen to their condition at o° C. The 67,300 calories represents the total energy change of the three chemical reactions H2 = H+H, 1/202 1/2(0+0), H+H+0 = H2O, when taking place at - 273° C. We cannot at present determine how much energy would be required by each reaction if it alone took place, but when a sufficient number of well-chosen chemical reactions have been thus studied it may be possible to find the key to all, and to determine not alone the force which acts between any two atoms, but the law which governs the distance apart of the atoms as well, and the exact amount of energy which will be given out by the different chemical and physical changes involved. A study of the energy changes accompanying, and the conditions necessary for, the dissociation of simple molecules should greatly aid in the solution of the problem. (To be continued). PROCEEDINGS OF SOCIETIES. CHEMICAL SOCIETY. Prof. PERCY F. FRANKLAND, LL.D., F.R.S., President, in the Chair. MESSRS. Hugh Marshall and C. H. K. Gonville were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. Fred Barrow, M.Sc., Ph.D., Birkbeck College, Breams Buildings, E.C.; David Brownlie, B.Sc., 41, Corporation Street, Manchester; Thomas Alfred Brunjes, 21 | Road, Garston, Liverpool; Jyotish Chandra Ghosh, 105, M. C. Ghosh's Lane, Howrah, India; Richard Ernest Gibbins, Clytha, Quinton Road Coventry; Rupert William Pope, B.Sc., 10 Malpas Road, Brockley, S.E.; Howard Vincent Potter, Rosemount, Pollard Road, Whetstone, N.; Alfred Reginald Roberts, care of Canada Cement Co., Shallow Lake, Ontario; Richard Smith, 6, Essex Road, Gorton, Manchester; John Kerfoot Wood, D.Sc., 7, Airlie Terrace, Dundee. A certificate has been authorised by the Council for presentation to ballot under By-law I. (3) in favour of John Duncan, Victoria Street, Waterloo, Sydney, N.S.W. : The PRESIDENT announced that the Longstaff Medal (1912) had been awarded to Dr. H. Brereton Baker, F.R.S.; the actual presentation would be made at the Annual General Meeting of the Society in March, 1912. Of the following papers those marked * were read :*333. "Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part II. The Rotations of some Secondary Alcohols containing the Isopropyl Group.” By ROBERT HOWSON PICKARD and JOSEPH KENYON. The authors have continued their investigations (Trans., 1911, xcix., 45), and six alcohols of the general formula CHMe2 CH(OH) R, where R-methyl, ethyl, n-propyl, n-amyl, n-hexyl, or n-octyl, were described. The specific rotations at 20° of the dextrorotatory forms these alcohols are:-Methylisopropylcarbinol, [a] D + 48°; ethylisopropylcarbinol, [a] D +151°; propylisopropyl carbinol, [a] D +21·2°; n-amylisopropylcarbinol, [a]D +227°; n-hexylisopropylcarbinol, [a] D +215°; and noctylisopropylcarbinol, [a] D +18.5°. *334. "The Alcohols of the Hydroaromatic and Terpene Series. Part II. The Menthols corresponding with Optically Inactive Menthone." By ROBERT HOWSON PICKARD and WILLIAM OSWALD LITTLEBURY. The authors described an investigation of the relationship existing between the menthols produced by the reduction of one of the two optically inactive stereoisomerides, which have the formula CHMe CH2 CH2 CH2-CO >CHPI. The accompanying diagram shows the results obtained. d-neoMenthol was found in some residues which were kindly presented to the authors by Messrs. Schimmel and Co., who obtained the same after working up large quantities of Japanese peppermint oil for l-menthol. water. 338. "Studies in the Camphane Series. Part XXXI. cinchonine, quinine, and their isomerides (Trans., 1911, | suitably arranged apparatus. The interaction of the xcix., 1254), it was shown that the absorption spectra of nascent hydrogen and nitric acid results in the ready cinchonine and quinoline are practically identical, the decomposition of the acid and formation of various reducreduced half of the cinchonine molecule having little effect tion products, the free oxygen being wholly converted into on the spectrum. The absorption spectra of quinine and cupreine have now been compared with those of 6-methoxyquinoline and 6-hydroxyquinoline, with similar results. The four spectra resemble one another very closely. They exhibit three bands each, the principal band having its head at about 1/3050, and the two others at about 1/A3500 and 1/A3750 respectively. The chief difference between the spectra of quinine and cupreine on the one hand, and those of methoxyquinoline and hydroxyquinoline on the other, lies in the somewhat greater absorption exhibited by the alkaloids. The hydrochlorides of quinine and 6-methoxyquinoline also yield absorption spectra which are nearly identical. Those given by N/100 solutions of quinine sulphate and methoxyquinoline sulphate (both fluorescent solutions) differ only in the greater general absorption of the former. *336. "Amino-derivatives of Arylsulphonanilides and Arylsulphon-3-naphthalides." By GILBERT T. MORGAN and FRANCES M. G. MICKLETHWAIT. The toluene-p-sulphonyl derivatives of the m- and pnitroanilines are readily methylated with methyl halides in alcoholic soda or potash, and the corresponding as-toluenep-sulphonylmethyl-m(and p)-phenylenediamines are produced by the reduction of these toluene-p-sulphonylmethylnitroanilines. The diazonium salts of the new bases furnish azo-colours dyeing on wool or silk by coupling with various naphtholsulphonic acids. also Toluene-p-sulphon-3-naphthalide yields on nitration not only toluene-p-sulphonyl-1-nitro-B-naphthylamine, but toluene-p-sulphonyl-1: 6-dinitro- ẞ-naphthylamine. The former of these nitro-derivatives is readily methylated, the latter only with some difficulty. The amines produced by reducing these nitro-compounds and their alkyl derivatives were described, together with a similar series of compounds derived from 8-naphthyl amine-6-sulphonic acid. "The Action of Nascent Hydrogen on Nitric 337. Acid." BY MARINDRA NATH BANERJEE and SATISH CHANDRA BANERJEE. Veley, in explaining the action of nitric acid on metals (Proc. Roy. Soc., 1890, xlvi., 216; 1893, lii., 27; Phil. Trans., 1891, A, 312; Fourn. Soc. Chem. Ind., 1891, x., 204), states that the action is due to nitrous acid and to its mass present in the solution. He believes that the action is started with mere traces of nitrous acid, always present in the original acid. He is not in favour of the nascent hydrogen theory advanced by certain chemists. The authors find that nascent hydrogen has rapid action on nitric acid, first decomposing it (acting catalytically), and then reducing it to the lower oxides of nitrogen, and finally to ammonia. This argument has been further extended to explain the action of nitric acid on metals, in which the authors have attempted to prove that it is the nascent hydrogen, and not nitrous acid, that is responsible for the formation of various reduction products. The reaction is found to depend entirely on the capacity of metals to decompose water, and the authors confirm the views of Montemartini as to the relation of the action of nitric acid on metals to that of metals on water (liberating hydrogen), namely, that those metals which decompose water at a high temperature give with nitric acid, nitrogen peroxide, trioxide, and dioxide; whilst those that decompose water at a low temperature give, in addition to the above, nitrous oxide, nitrogen, and ammonia; and, lastly, those decomposing water at the ordinary temperature also evolve hydrogen. Nascent hydrogen was obtained from platinum-black which had occluded the gas. The experiments showing the interaction between nitric acid and the platinum-black on the one hand, and the absorption of the products by suitable reagents on the other, were conducted in a Nitromethylenecamphor, C8H14 , prepared from camphorquinone and sodionitromethane in alcohol, melts at 77, and is immediately resolved into its factors by warm aqueous alkali; under certain conditions it is accompanied by nitromethylhydroxycamphor, C(OH)·CH2 NO2 C8H14 which melts at 104°, and also gives camphorquinone with hot alkali hydroxide. Ethyl camphorylidenecyanoacetate (ethyl methylenecamphorcyanoC:C(CN) CO2 C2H5 carboxylate), C8H14 produced by CO camphorquinone and phenylacetonitrile with a small proPportion of sodium ethoxide, crystallises in massive yellow prisms, melting at 166°. When ethyl camphorylidenecyanoacetate is treated with hydrogen peroxide, hydrolysis of the cyano-group takes place simultaneously with oxidation. The resulting amideester, C15H21O6N, melts at 209°, and is accompanied by the amide-acid, C13H17O6N, H2O, melting at 205°. Both substances, on complete hydrolysis, yield the dibasic acid, C13H1607, which melts at 231°. 339. "Solutions of Halogen Double Salts in Water and Ether." By JAMES ERNEST MARSH. The capability of the halogen double salts to give homogeneous solutions in a mixture of ether and water is limited, on the one hand, by the too great solubility of the salt in one of the solvents, and on the other by the too slight solubility of the salt in both solvents. Sodium, potassium, rubidium, and barium mercuri-iodides give with ether and water homogeneous solutions, which on warming separate into three layers; the lithium and ammonium salts are very soluble in ether with a little water, and leave the excess of water undissolved; the cæsium salt is only sparingly soluble, and has but little effect on a mixture of Of the bromides, ammonium mercuriether and water. bromide, and of the chlorides, lithium mercurichloride are the only inorganic salts of this sort which have been found to give homogeneous solutions, separating on warming into three layers. Potassium mercurichloride resembles cæsium mercuri-iodide, and has but little action. So far as they have been examined, the salts of primary amines resemble the salts of ammonium, whilst tetramethylammonium mercuri-iodide resembles the cæsium salt, and has even less action. CHEMICAL NEWS, Determination of Sulphur in Petroleum between the absorptive properties of solution of metals In extension of previous work, which dealt with salts in acid solution (Trans., 1911, xcix., 1132), measurements have been made of the solubility at 30° of oxalic acid in solutions of nitric and of hydrochloric acids. In both cases the solubility falls to a minimum as the concentration of solvent acid rises, after which it increases. In nitric acid solutions this increase is terminated by conversion of the solid oxalic acid into the anhydrous compound, the solubility of which then falls to a second minimum. The concentration of nitric acid at the transition point is about that of "constant boiling-point❞ acid. The solubility curves of the dihydrate in both acids are conic in form, and in this respect resemble certain other solubility curves. The assumption of constant molecular volume in solution, which was found to be valid in the earlier cases studied, holds also in these instances. 23 point. The first portion of the paper related to the Supplementary determinations were made with B-naph-case of the X-rays-a factor which quickly reduced their apparent advantage over the rays of radium-Mr. Russ came to the following conclusion:-In equivalent times the same biological effect per square cm. of tissue on the surface ought to be obtained by an exposure to B-rays of radium corresponding to 2.75 mgrms. of radium bromide as by the exposure of X-rays from an unscreened bulb working at 9 cm. spark-gap, with a distance of 10 cm. between the anode and the tissue. The author described a method by which a large sample may be concentrated by treatment with fuming nitric acid and potassium bromide, the product being absorbed by magnesium oxide, which enables it to be readily removed from the concentrating dish, and burnt in the Parr apparatus with sodium peroxide. Several samples may be treated simultaneously, the final combustion taking about forty-five seconds. Test analyses were given, comparing results with the Mahler bomb method. For samples poor in sulphur a modified lamp method was described, in which a large sample is completely burnt, thus avoiding the errors in the usual method owing to the sulphur being given off in an irregular manner. Some Mexican and Texan kerosenes contain loosely combined sulphur, which decomposes when heated or when in contact with some metals, such as copper; since samples have been known to blister, and even perforate, a copper lamp, the testing of commercial kerosenes for such unstable sulphur was recommended. The author described a qualitative and quantitative method for the purpose. For the manipulation of the small precipitates of barium sulphate obtained in these operations, the author described a rapid suction-filter method, in which the amount of filter paper is reduced to a minimum, and the weighing conducted in a very light dish. For the simultaneous treatment of several precipitates a special arrangement of the apparatus was described. RÖNTGEN SOCIETY. AT the meeting of the Röntgen Society on January 2nd, Mr. SIDNEY RUSS, B.Sc., of the Cancer Rosearch Labora tory, Middlesex Hospital, gave what was apparently something in the nature of an interim report upon X-ray and Radium Measurements and Comparisons. Part of the object of the investigations was to determine whether, with an X-ray bulb, it would be possible to obtain any sort of equivalent in terms of B- and y-rays from a definite NOTICES OF BOOKS. Allen's Commercial Organic Analysis. Volume V., Fourth ALTHOUGH the fifth volume of "Allen's Commercial Organic An Experimental Course of Physical Chemistry. Part I. THIS book will certainly find a hearty welcome in |